Water-insoluble azo-dyestuffs and fiber dyed therewith



ides of 2,3-hydroxy-naphthoic acid Patented May 7, 1935 UNITED STATES PATENT" OFFICE 1 17V. A,'.lEl -INSOLUBLE AZO-DYESTUFFS AND FIBER DYED THEREWITH No Drawing. Application January 9, 1934, Serial 7 No. 705,970. In France January 12, 1933 14 Claims.

The present invention relates to water-insoluble azo-dyestufis and to fiber dyed therewith.

- We have found that valuable water-insoluble azo-deystuffs are obtainable by combining arylof the following formula: j

on V t 7 CHI 7 V (JO-NEGO -Allql with diazo, tetrazo or diazoazo compounds which do not contain sulfonic acid or carboxylic acid groups. V .7 V, a The new dyestuffs correspondto the following general formula: n

onfl '1. 'i

MHGM.

wherein vR. stands for a ra'dialof the benzene, naphthalene, diphenyl, carbazole or anthraquinone series and n means, the number .1 or 2.1 They have the most varied shades and are distinguished by their very good fastness properties.

stufis; they may also. be producedf on the veg,-

etable or animal fiber, by printing or according" to the ice color method.

The methylbenzene-4-alkylethers) used as coupling components may be prepared by condensing 2,3- hydroxynaphthoic acid with l-amino-2,5-dimethylbenzene 4 alkyl ethers according to known methods, for instance, in toluene with addition of phosporus trichloride. 2,3- -hydroxynaphthoyl -(1-amino-4-methoxy 2,5 dimethylbenzene) crystallizes from chlorobenzene inthe- They may be used for the preparation of pigment dye- 2,3-hydroxynaphthoyl-(l-amino-2,5 di- 1.14.2 grams of l amino-2 methyl-5-chlorobenzene are diazotized in known manner and the diazo solution is coupledwith a solution of 35 grams of 2,3 -'hydroxynaphthoyl (1 amino 4 methoxy-2,5-dimethylbenzene) in dilute caustic soda solution which has been mixed with Turkey red oil and aquantity of sodium acetate which is suflicient for binding the excess of mineral acid. The dyestufiwhich precipitates has the following formula: 7

G a 01 s OH on.v

MHQOCH. I 5 Hz 7.

It is filtered and well washed. In order to prepare pigment dyestuffs therefrom it is advantageously used'in the form of a paste and furnishes, when mixed with a suitable substratum, a red lake of very good fastness, properties. I 2. Well boiled and dried cotton yarn is impregnated with a solution of 6 grams of 2,3-hydroxynaphthoyl (l amino 4 methoxy 2,5.- dimethylbenzene) 12 cc. of caustic soda solution of 34-B. and 12cc; of Turkeyred oil per liter. The material is thoroughly squeezed and developed in a diazo solution, neutralized with sodium acetate, containing 1.68 grams of l-amino-Z- methoxy-*i-nitrobenzene per liter, then rinsed and soaped at boiling temperature.

-A currant shade of very good fastness properties is obtained. The dyestuff has the following formula: 7

C O-NH OOH:

3. Suitably pre-treated cotton yarn is impregnated with asolution of 5 grams of 2,3-hydroxynaphthoyl (1 amino 4-'methoxy"-2,5-dimethylbenzene), 10 cc. of caustic soda solution of 34 B. and 10 cc;:of Turkey red oil per liter. ,The material is thoroughly squeezed and developed in a diazo solution, neutralizedwi'thsodium acetate, containing perliter 2.9 grams of l-amino-Z- methoxybenzene 5 sulfonyldiethylam'ine, then well rinsed and soaped at boiling temperature. A clear bluish-red dyeing is obtainedof very good fastness properties.

. The dyestuff the following formula:

OOH: O N

I Call: CH 5300/ I (hHs I OCH! The followingv table describes a further number of azo-dyestufis according. to this invention.

naphthalene; diphenyl, carbazoleor anthraquinone series and 11. means the number 1 or 2, yield- ,ing, when produced on the fiber, dyeings of various shades and very good fastness properties.

2. The water-insoluble azo-dyestufis of the following general formula:

1 N===NR CH: CO-NHGO-elkyl c rn wherein R stands for a radical of the benzene,

naphthalene, diphenyl, carbazole or anthraquinone series, yielding, when produced on the fiber, dyeings of various shades and very good fastness properties.

Diazo compound from Coupling component Shade l-amino-li-ehlorob one 2,3 hydroxynaphthoyl- '(1 amino Red.

4-methoxy-2,5-dnnethylbenzene). 1-amino-2-methyl-4-chloro do Do. l-amino-2-methyl-3-chlorobenzene do Do. l-amino-2-methy1-5-nitrobenzene D0. l-amino-2-methoxy-5-nitro do Scarletred. l-amino-4-methyl-2-nitro do Bordeaux red. 1-amino-4-chloro-2-nitrobenzene 1 do Deep red l-amino4-methoxv-2-nitro do Garnet. 1-amino-4-benzoylamino-2 niethoxy fi-methylbenzened o ,Red. violet. 1-amino-4-benzoylammo-2,5-d1methoxyh o1 nn do Reddish blue. 1-amino-4-benzoylan1ino-2,5-diethoxy one do Do. l-amino-4-benzoylamino-5-methoxy-2-methylbenzene. do Violet. 1-an1ino-4-benzoylamino-5-methoxy-2'chlorobenzene. do 7 Do. l-aznino-i-acetylamino-S-methoxy-Z-phenoxybenzen do Bluish Bordeaux red. 1,4-diamino-2,3-dimethyl-6{br0n1obenzene do Do. 4-amino-3,2-dimethyl-azobenzene Grenade. 4-a1nino-2,&dimethoxy-4-mtroazobenzene do Reddish black. 1-amino-4-(2-ethoxy-phenyl-1-az0)naphthalene; do Black. 7 4,4-diamino3,3-dimethoxydipheny do Blue. l-aminoi-benzoy1amino-2,5 one do Bordeaux red. 1-amino-2-methyl-benzene-5-sulfonyl-diethylamino do Clear yellowish red. i-amino-2-methoxy-benzene-5-sulfonylbenzylmethylamine.. do Bluish red. 1 amino-2'ethoxy-benzene-fi-sulfonyl-diethylamine. do Clear bluish red. 1-amino-3-benzoyl-benzene.r do- Yellow red. l-amin0-2,4,5-trichloroone do Brown red. 3-a1m'no-4,4-diehloro-diphenyl do .Red. I l-amino-2- henoxy-5-chlorobenzene. do Do. 1-amino-2- 2,5-dieh.lorohenoxy)-5'chlorobenzene do Yellowish red. l-amino-2-phenylsulfony b v do Red orange. l-amino-2-chloro-5-trifluormethylbenzenedo Brown red. 2-amino-1,o-dibromomapht e do Blue red. 3-amino-carbazolcdo Dark violet. 2,7-diamino-car v l do Black blue. 4,4-diamino-3,3-dichlorodiphenyl do Currant. 1-an1ino-2-nitr n do Bordeaux red. 1-amino-2,5-dichloro-b moo do Orange brown. l-amino-anthraq do Brown red. 2,(i-diamino-anthrag jn n do Bluish red. l-amino-2-methyl-4-mtrobenzeno do Bluish Bordeaux. l-amino-2-1nethoxy-4-nitrob one do Currant. 1-amino-2-chloro-b n 2.3-hydroxy naphthoyl-(l-amino-Math- Red brown.

oxy-2.5-d1methylbenzene). i

1-amino-2,4,5-trichloro-benzenedo Brownish red. l-amino-3-n1ethyl-4,6-d1chlorohnn mm dn Yellowish red. l-a1nino-2-phenoxy-S-chlorob do/ Bluish red. l-ainino-2-methyl4-bromo-5-chlorob D0. l-amino-Z-nitrnnnilim fin Deepred 1 1amino-2-methyl5-nitro-b do Yellowish red. 4-am1no-3-methoxy-6,4-dimethyl-2'-nitraazob ene do Dark current.

We claim: 1. The water-insoluble azo-dyestufis of the following general formula:

wherein R stands for a radical of-the benzene,

I 3. The water-insoluble azo-dyestufis lowing general formula:

of the folwherein R stands for a. radical of the benzene series, yielding, when produced on the fiber, dyeings of various shades and very good'fastness properties. I.

yielding, when produced on the fiber, a bluish red dyeing of good fastness properties.

7. The water-insoluble azo-dyestufi of the following formula:

4. f'he water-insoluble azo-dyestufis of the following general formula:

CH: 0 o-mrjo on.

wherein R stands for a radical of the benzene series. yielding, when produced on the fiber, dyeings of various shades and very good fastness properties.

5. The water-insoluble azo-dyestuff of the following formula:

OzN N=N CH; 0 ONH3O CH:

yielding, when produced on the fiber, a bluish 0H: CONHQOCH: H:

yielding, when produced on the fiber, an orange brown dyein g of good fastness properties.

8. Fiber dyed with the azo-dyestufis as claimed in claim 1.

9. Fiber dyed with the azo-dyestuffs as claimed 20 in claim 2.

10. Fiber dyed with the azo-dyestufis as claimed in claim 3.

1 1. Fiber dyed with the azo-dyestuffs as claimed in claim 4.

12. Fiber dyed with the azo-dyestufi as claimed in claim 5.

13. Fiber dyed with the azo-dyestufi as claimed in claim 6.

14. Fiber dyed with the azo-dyestufi as claimed in claim 7.

ARTHUR ZITSCHER. WILHELM LAMBERZ. 

